New vat dyestuffs

ABSTRACT

Vat dyestuffs of the formula   wherein X represents a nitrogen-containing heterocyclic radical which is bonded through a carbon atom, R1 and R2 each represent a hydrogen atom or a low molecular alkyl radical, and A1 and A2 represent a different or similar vattable radical with 3 to 6 condensed rings, are suitable for dyeing and printing the most varied materials, in particular to dyeing and printing fibres made from natural or regenerated cellulose in the presence of reducing agents.

United States Patent Oct. 28, 1975 Altermatt NEW VAT DYESTUFFS [57] ABSTRACT [75] Inventor: Hans Altermatt, Reinach,

Switzerland Vat dyestuffs of the formula [73]- Assignee: Ciba-Geigy AG, Basel, Switzerland 22 Filed: Jan. 10, 1974 A,N-c N-A2 [21] App]. N0.: 432,255

R, N R2 [30] Foreign Application Priority Data I Jan. 30, 1973 Switzerland 1326/73 X 2% 8 260/249; 8/ wherein X represents a nitrogen-containing heterocyd 26O/249 clic radical which is bonded through a carbon atom, 1e o are R1 and R2 each represent a hydrogen atom or a low molecular alkyl radical, and A and A represent a dif' [56] References cued ferent or similar vattable radical with 3 to 6 con- UNlTED STATES PATENTS densed rings, are suitable for dyeing and printing the 2,729,638 1/1956 Joyce 260/249 most varied materials, in particular to dyeing and ,800,468 7/1957 Scalera et a1. 260/249 X printing fibres made from natural or regenerated cel- JOyC lulose in the presence of reducing agents 2,832,779 4/1958 Ebel et al 260/249 X Primary Examiner-John M. Ford Attorney, Agent, or' Firm-Joseph G. Kolodny;

Prabodh I. Almaula; Edward McC. Roberts 3 Claims, No Drawings NEW VAT DYESTUFFS wherein X represents a nitrogen-containing heterocyclic radical which is bonded through a carbon atom, R and R each represent a hydrogen atom or a low molecular alkyl radical, and A and A represent a different or similar vattable radical with 3 to 6 condensed rings. Possible radicals R and R are alkyl groups with l to 4 carbon atoms, e.g. methyl, ethyl, propyl, or isopropyl groups, as well as preferably hydrogen atoms.

Possible vattable radicals A and A are radicals of polycyclic compounds, such as anthrapyramidines, anthrapyridones, anthrapyrimidones, azabenzanthrones, benzanthrones, anthranthrones, anthrimides, isothiazole-anthrones, pyrazoleanthrones, pyrimidanthrones, anthraquinone compounds which are derived from 9,10 -dioxoanthracene and optionally contain further fused carbocyclic and heterocyclic rings, such as quinazoline-anthraquinones, oxazole-anthraquinines, thiazoleanthraquinones, oxadiazole-anthraquinones, pyrazoleanthraquinones, pyrazino-anthraquinones, and, preferably, 3,4-phthaloylacridones bonded in 2- or 8-position as well as radicals of anthraquinones bonded in lor 2-position. All these radicals can carry the customary substituents for vat dyestuffs. Examples of such substituents are: halogen atoms, in particular chlorine, fluorine, or bromine alkyl, alkoxy, aryl, aryloxy, aralkyl, aralkoxy, arylamino alkylmercapto, arylmercapto, cyano and thiacyano groups. Throughout this specification, the term alkyl refers in particular to radicals with l to 4 carbon atoms, and aryl denotes in particular radicals such as phenyl, tolyl, chlorophenyl, methoxyphenyl, or naphthyl radicals, and aralkyl means in particular the benzyl radical. Particularly important substituents are moreover the acyl and acylamino group. The term acyl comprises above all radicals of aromatic carboxylic or sulphonic acids, in particular those of the benzene series, or low molecular alkanoyl or alkylsulphonyl radicals (i.e. which contain from 1 to 4 carbon atoms), e.g. the acetyl, benzoyl, pchlorobenzoyl, p-phenylbenzoyl, benzenesulphonyl or p-toluenesulphonyl radical, also low molecular carbalkoxy radicals and sulphonamide'or carboxy amide groups the nitrogen atom of which can be substituted by alkyl or aryl radicals, e. g. the carboethoxy, carbamoyl or sulphamoyl radical.

Possible radicals represented by X are the radicals of the following N-heterocycles: pyridine, pyrimidine, pyridazine, pyrazine and quinoline, which can be substituted by alkyl, aralkyl, alkoxy, aryloxy, alkylamino, arylamino, alkylmercapto, arylmercapto or halogen atoms, in particular chlorine and bromine.

Particularly important dyestuffs are those in which X represents a pyridine radical which can have the substituents mentioned hereinabove.

Preferred dyestuffs are therefore those of the general formula 10 wherein A and A represent an anthraquinone radical bonded in lor Z-position or a 3,4-phthaloylacridone radical bonded in 2- or 8-position, and A and A and the pyridine radical can carry the indicated substituents.

The dyestuffs are manufactured by reaction of 2 moles of a compound of the formula or of a mixture of both, with a triazine of the formula R g SR B or 2 moles of a compound of the formula A NHR or A -NHR or any mixture of the two, with 1 mole of the compound of the general formula N I! Halogen(f fi-Halogen N N T/ x The mixture of the vattable compounds can be used simultaneously or stepwise. By means of such combinations it is possible to obtain mixed shades.

These methods of manufacture are widely known. If the first method is followed, A -halogen, A -halogen and diaminotriazine, it is advantageous to use a culpyridine catalyst as described in French Patent 1,603,058. In this case, examples of suitable starting 2-propyl-6-chloro-4-pyridyl materials A -halogen and A -halogen are haloan- Z-pyrimidyl,

thraquinones, i.e. both 04- and B-haloanthraquinones, 4-pyrimidyl,

for example: S-pyrimidyl,

1-chl0r0an hr q inn If dihalotriazines and compounds of the formula 1,3-dichloroanthraquinone, A -NHR or A NHR are used as starting materials, l,S-dichloroanthraquinone, then instead of the haloanthraquinones there are used l,6-dichloroanthraquinone, by analogy the corresponding 0:- or B-aminoanthraqui- 1,8-dichloroanthraquinone, nones, for example: l-bromoanthraquinone l0 l-aminoanthraquinone 1,5-dibromoanthraquinone, 1-amino-4-methoxyanthraquinone, 1 ,S-dibromoanthraquinone, 1-amino-4-acetylaminoanthraquinone, 2- hl r n hr q in 1-amin0-4-benzoylamino-anthraquinone 2,6-dichlol'oaflthl'aquinonei 1 -amino-4-(p-tolylsulphonylamino-anthraquinone, 2,ldichloroamhraquinonea l -amino-4-(p-chlorobenzoylamino)-anthraquinone, Lbromoamhraquinone, l -amin0-4-anilido-anthraquinone, 2fi-dibromoamhraquinone, 1 -amino-4-[ p-( N,N-dimethylsulphamido Zldibromoamhraquinone, benzoylamino]-anthraquinone, 1-hlQw-5+10etylaminoamhraquinone9 1 -amino-4-phenylmercapto-anthraquinone, l-chloro-4-benzoylaminoanthraquinone, 4' i l-chloro-4-(p-chlorobenzoylamino )-anthraquinone anthraquinone 1-bromo-4-benzoylaminoanthraquinone, 1 amino 4 chloroanthraquinone, "p y as well as the corresponding l-aminoanthraquinones anthraquinone, which are substituted in the 5- or 8-position instead of l-chloro-5-benzoylaminoanthraquinone, in 4130mm. l-chloro-S p-chlorobenzoylamino )-anthraquinone Laminoanthricluinone 1 bromo-5-benzoylaminoanthraquinone, 1 amin0 2 methyl anthraquinone, 1-chloro-2-methylanthraquinone, 1 amino 3 chloro amhraquinone, 1 P 1 -amino-6,7-dichloro-anthraquinone, l'chloro4'methoxyamhraqulnone l -amino-6-phenylmercapto-anthraquinone, 1'bromo'z'methoxyamhraqufnone l-amino-7-phenylmercapto-anthraquinone, 1memo-4 methoxyantpraqumone 1-amino-6-chloro-7-phenylmercapto-anthraquinone, 1emote-3'acqyHt-ammo-ap thraqumone 1 -amino-7-chloro-6-phenylmercapto-anthraquinone, m j g r g 1 ,4-diamino-2-acetyl-anthraquinone,

c mercaptoant raquinone 2-amino-3-chloro-anthraquinone, l-chl0r0-5-phenylmercaptoanthraqumone, 2 amino 4 Chloro amhraquinone 2-chloro-3,4-phthaloylacr1done, 2 Chl0ro amhra uinone 2,5,7-trichloro-3,4-phthaloylacridone, 1 q l chlorobenzamhrone -am no-6-chloro-anthraqumone,

4O 1-ammo-3-chloro-6-methyl-anthraqumone bzl -bromobenzanthrone, 6-bzl -dichlorobenzanthrone, 6-bzl -dibromobenzanthrone, dichloroanthranthrone,

l-amino-2-methyl-3-chloro-anthraquinone, 1-amino-7-chloro-anthraquinone, 2-amino-3,4-phthaloylacridone,

2-amino-6- or 7-chl0ro-3,4-phthaloylacridone,

gggigxggzrgg lgggf 2-amino-6-trifluoromethyl-3,4-phthaloylacridone,

tribromopyramhmne' 2-amino-5,7-dichlor0-3,4-phthaloylacridone,

Suitable diaminotriazines are e.g. those of the forz'amfno'l7'dlchloro'3'4'phthaloy!acrldone mula 8-ammo-5-chloro-3,4-phthaloylacr1done,

7-aminol ,2-benzo-5 ,6-phthaloylacridone, aminoanthranthrone,

aminoisothiazolanthrone Examples of suitable dihalotriazines, wherein hal" H2N -NH I represents chlorine or bromine, are:

l N X halC Chal wherein IL I I X= 2-pyridyl, 3-pyridyl, f 4-pyridyl, X 5-ethyl-2-pyridyl, 2-chloro-3-pyridyl, in which X has the same meaning as given for the 4-methyl-3-pyridyl, diaminotriazines cited hereinbefore. 2-chloro-4-pyridyl, The products according to the invention are suitable 2-methyl-4-pyridyl, for dyeing and printing the most varied materials, in

2,6-dimethyl-4-pyridyl, particular for dyeing and printing fibres made from natural or regenerated cellulose in the presence of reducing agents, e.g. dithionite.

The dyeing which are obtained are characterised by outstanding levelling properties. The fastness properties are in general very good, in particular the fastness 5 to light, water, chlorine, and to boiling soda. The new dyestuffs reserve polyester fibres well or stain themtone, in tone, which makes them suitable for dyeing fibre blends in admixture with disperse dyestuffs.

Compared with known comparable dyestufls, which instead of a heterocyclic radical, in particular the pyridyl radical, contain a phenyl radical bonded to the striazine ring, the dyestuffs of the present invention are characterised by a reduced fibre damaging action in light.

The new dyestuffs can also be used as pigments. On account of their favourable properties, they can be used for the most diverse forms of pigment application, e.g. in finely divided form for colouring rayon and vis-. cose, or cellulose ethers or esters, or polyamides or polyurethanes or polyesters in the spinning melt, as well as for the production of coloured lacquers or lake formers, solutions or products from acetyl cellulose, nitrocellulose, natural resins or artificial resins, such as polymerisation resins or condensation resins, e.g. aminoplasts, alkyd resins, phenolic plastics, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins. Furthermore, it is also possible to use them with advantage in the manufacture of coloured pencils cosmetic preparations, or laminated sheets.

The following Examples illustrate the invention, the parts being parts by weight unless otherwise stated.

EXAMPLE I A solution of 0.55 parts of copper (I) iodide in 3 parts of pyridine is added to a suspension consisting of parts of l-chloroanthraquinone, 3.75 parts of 2,4- diamino-6-(4'-pyridyl)-s triazine, and 5.3 parts of so dium carbonate in 70 parts of nitrobenzene and the whole is stirred over the course of 1 hour at 180185C. The mixture is subsequently stirred for 4 hours at this temperature. The reaction mass is cooled to 80C, filtered, and the residue is thoroughly washed with nitrobenzene, then with methanol and water. Any copper present is removed by stirring the yellow dyestuff in dilute nitric acid for one-half hour at 80C. It is then filtered off, washed neutral, and dried. Yield: 11.2 parts of a yellow dyestuff of the formula "6 umn l of the following Table of the compounds listed in column 11. 1

TABLE I 3,75 2,4-diamino-6-( 2'-pyridyl)-s-triazine 3,75 2,4-diamino-6-( 3 '-pyridy1)-s-triazine 4, l 2 ,4-diamino-( 4'-methyl-3 '-pyridyl )-s-triazine 4,4 2,4-diamino-(2'chloro-3'-pyridyl)-s-triazine 3,8 2,4-diamino-(5'-pyrimidy1)-s-triazine EXAMPLE 2 By substituting" .for .the 10 parts of 1- chloroanthraquinone in Example '1' the amount indicated in column I of the following Table of the anthraquinones listed in column ll, there are obtained dye stuffs which from the vat dye cotton in the shades listed in column III.

In place of the diaminotriazine' mentioned in Example 1, it is also possible to use with equal success the compounds listed in Table 1.

EXAMPLE 3 11.4 parts of l,3-dichloroanthraquinone and 3.75 parts of 2,4-diamino-6-(3'-pyridino)-s-triazine are stirred for 4 hours at 185C in the presence of 5.3 parts of sodium carbonate, 1 part of copper (l) iodide and 4 parts of pyridine in parts of nitrobenzene. The resulting yellow dyestuff is filtered off at C and processed as described in Example 1 to yield 12 parts of the dyestuff of the formula 1 The dyestuff, which is treated in' the conventional manner with sodium hypochlorite, dyes cotton from' the vat in brilliant greenish yellow shades which are fast to light and wet treatments. 1

A dyestuff is obtained which dyes cotton from the vat in neutral yellow shades by substituting 11.4 parts of 1,6- or l,7-dichloroanthraquinone for the 1 1.4 parts of 1,3-dichloroanthraquinone.

Dyeing Instruction I 1 Part of dyestuff is vatted at 5070C with 10 parts by volume of sodium hydroxide having a specific gravity of 36 Be and 5 parts of sodium hydrosulphite in 200 parts of water. The above stock vat is added to a dyebath which contains in 2000 parts of water 5 parts by volume of sodium hydroxide solution with a specific gravity of 36 Be and 3.7 parts of sodium hydrosulphite. 100 parts of cotton are put into this dyebath at 40C. After minutes, parts of sodium chloride are added and after minutes, a further 15 parts and dyeing is carried out for 45 minutes at 40C. The cotton is then squeezed out, oxidised, and finished in the conventional manner.

Dyeing Instruction 11 1 part of the dyestuff obtained according to Example 1 and 0.5 part of CI Disperse Yellow 84 are ground wet with 2.5 parts of a 50% aqueous solution of the sodium salt of dinaphthylmethane-disulphonic acid. A dyebath is prepared with this dyestuff preparation, 2 parts of ammonium sulphate, and 1000 parts of water, and the pH is adjusted to 6.0-6.9 with monosodium phosphate.

100 parts of a blended fabric of cotton/polyester (67% polyester) are put into this bath, which is heated to 120-125C over the course of 45 minutes. Dyeing is carried out at this temperature for 60 minutes in a sealed vessel. The dyebath is then cooled to 6070C and 20 parts by volume of sodium hydroxide solution of Be 36 and 5 parts of sodium hydrosulphite are added. After 45 minutes, the fabric is sequeezed out, oxidised, and finished in the usual manner. A blended fabric dyed yellow is obtained.

Pigment coloration 5 Parts of the dyestuff mentioned in Example 1 are mixed with 95 parts of dioctyl phthalate and ground in a ball mill until the dyestuff particles are smaller than 3p.

0.8 part of this dioctyl phthalate paste is mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate and 0.1 part of cadmium stearate, and this mixture is then rolled to and fro for 5 minutes in a twin roller mill at 140C.

A yellow coloured material having good migration properties and good fastness to light is obtained.

Coloration of lacquers consisting of 26.4 g of coconut alkyl resin, 24.0 of melamine formaaldehyde resin (50% solids content), 8.8 g of ethylene glycol monomethyl ether, and 28.8 g of xylene.

By spraying this varnish on an aluminium sheet, drying it for 30 minutes at room temperature and then stoving it for 30 minutes at C, there is obtained a clear red finish of good tinctorial strength which is characterised by good fastness to crosslacquering, outstanding fastness to light, and good resistance to weathering.

I claim:

1. A vat dyestuff of the formula wherein X is pyridyl or pyridyl substituted by alkyl of 1 to 4 carbon atoms or is pyrimidyl, which is bound through a carbon atom, and

A and A each is independently anthraquinonyl or anthraquinonyl substituted by halo, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, alkanoyl of l-4 carbon atoms, amino, alkanoylamino of l-4 carbon atoms, phenylamino, benzoylamino, p-chlorobenzoylamino, phenylmercapto, ptolylsulphonylamino, p-(N,N-dimethylsulphamido) benzoylamino, or p-(phenyl)benzoylamino; or is 3,4-phthaloylacridonyl or said phthaloylacridonyl substituted by halo 0r trifluoromethyl, and bonded via the 2- or 8-position. 2. A vat dyestuff as claimed in claim 1, wherein X is pyridyl, and

A and A is anthraquinonyl or anthraquinonyl substituted by halo, alkyl of l-4 carbon atoms, alkoxy of l4 carbon atoms, alkanoyl of 1-4 carbon atoms, amino, phenylamino, benzoylamino, pchlorobenzoylamino or phenylmercapto; or is 3,4- phthaloylacridonyl which is bonded via the 2- or 8-position. 3. A dyestuff as claimed in claim 2 of the formula NH(II C NH CO N a CO CO CO 

1. A VAT DYESTUFF OF THE FORMULA
 2. A vat dyestuff as claimed in claim 1, wherein X is pyridyl, and A1 and A2 is anthraquinonyl or anthraquinonyl substituted by halo, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, alkanoyl of 1-4 carbon atoms, amino, phenylamino, benzoylamino, p-chlorobenzoylamino or phenylmercapto; or is 3,4-phthaloylacridonyl which is bonded via the 2- or 8-position.
 3. A dyestuff as claimed in claim 2 of the formula 